Fixing composition and method of aftertreating dyed materials



Patented Aug. 17, 1937 PATENT "OFFICE FIXING COIVIPOSITION AND METHOD OFAFTERTREATING DYED MATERIALS Edward S. Chapin and Walter C. Duriee,

' 1 Boston, Mass.

No Drawing. Application December 15, 1936, Serial N0. 115,982

23 Claims; (01. 8-5) This invention relates to a fixing composition foruse in, and also to a method of, aftertreating' dyed materials, andespecially dyed union materials, to fix the colors.

The invention has for an object to provide a novel fixing compositionwhich in solution is capable of use with advantage to aftertreat dyedmaterials, and especially dyed union materials, and-to produce resultantmaterials in which the colors are fast to water, to wet hot pressingagainst white fabrics, sometimes to perspiration, and to otherconditions involving the action of water, steam, and saline solutions.

A further object of the invention is to provide a novel and improvedprocess oftreatingdyed materials, and especially dyed union materials,in order to fix the colors thereof to render them fast to water, to wethot pressing against white fabrics, sometimes to perspiration, and toother agencies which involve resistance to the action of .water, steam,and saline solutions.

A further object of the'invention is to providevide a novel and improvedfixing composition for,

and a method of,.aftertreating dyed materials, and especially dyed unionmaterials, whereby the colors of the dyed materials can be fixed atordinary supply water temperature.

With these objects in' view and such others as may hereinafter appear,the invention consists in the fixing composition and compositionshereinafter described together with the process of treating dyedmaterials, and especially dyed union materials, hereinafter described,and as particularly defined in the claims at the end of thisspecification.

Thepermlanency' of color in dyed fibers as to resistance to water, towet hot pressing against "white, to crocking, to perspiration, andto'other similar conditions which involve resistance to steam and salinesolutions, is of great importance to the textileindustrles. 7

Especially is this true, of materials and/or fabrics having mixedfibers, such-as goods made 5 from a combination of cotton and wool andsimilar materials and/or fabrics which may also contain rayon, silk, andother fibers. With these union materials and/or fabrics the securing ofwater fast results has prior to our inventionm required long andcomplicated processes, frequently resulting in off shade colors and theproduction of seconds. Aftertreatments have some times been utilized butthese change the shade of the dyeings or otherwise injure the-goods, and15v have not, in general, made the materials and/or fabricssatisfactorily water fast.

to the medium and lower priced trade and accordingly the practise hasbeen to use low priced,

though unfast, union dyes. These union dyes 25 are essentially mixturesof substantive (direct) dyes for coloring the cotton and the wool, aswell as other fibers receptive to such dyes, and neutral dyeing (acid)dyes for coloring and toning the wool, as well as other fibers receptiveto such dyes. 30 The method ,of dyeing union materials as or- I dinarilypractised consists in running thematerials and/or fabrics in .a dyesolution in the presence of common salt, and also adjusting thetemperature of the dye-bath during the operation. The cotton andsimilarly acting fibers of the fabric take the direct dye in the mainbelow the boiling point, and the wool and similarly acting fibersrequire more nearly a boiling for dyeing. .The final step in such aprocess is to wash 40 the goods in an attempt to remove the excess andunused dye. However, the results obtained are dyed products that are notfast to steeping in water, to wet hot pressing against white, toperspiration tests, and to other conditions.

Thus, the great majority of commercial fabrics of mixed fiberscontaining cotton, as men's wear suitings, meltons, satinets; ladiesdress goods, ladies cloakings,v ski-clothes, linings, etc., have notbeen dyed by the so-called union dyes prior 50 to our invention in sucha manner as to make them fast to water, to wet hot pressing, toperspiration, and to other conditions. As a result, I where such dyedproducts were made up into garvii ments, the wearers experiencedstaining of underneath garments and even of the body when the dyedgarments became wet; and serious difficulties resulted in repressing thewet garments from the looseness of the color.

The present invention contemplates a novel fixing composition which isparticularly useful in practising a process for fixing the-dye or colorin dyed materials, and especially dyed union materials, and whichinvolves the aftertreatment of dyed materials, and especially dyed unionmaterials, in order to fix the dye and render it fast to water, to wethot pressing against white "fabrics, sometimes to perspiration,sometimes to wet and dry crocking, and to other conditions involvingresistance to the action of water, steam, and saline solutions.

The aftertreatment of dyed materials, composed of one individual fiberor of a mixture of fibers, is not new. Various water soluble metallicmixed fabrics containing vegetable fiber, fre-' quently in deteriorationof the fabric. Accordingly aftertreatments of dyed materials had beenpractically abandoned by the art prior to our 40 invention except forthe use of bichrome to aftertreat or top-chrome dyed materials toimprove fastness to washing", fulling, and light.

The specific requirement of fastness to water and to wet hot pressingagainst white fabrics,

especially for dyed union goods, is of comparatively recent origin inthe art and the trade. Our invention, as above set forth, comprises anovel fixing composition and a novel method of aftertreatment, which isspecially designed to fix the dye or color in .dyed materials, andespecially dyed union materials, to water and to wet hot pressingagainst white fabrics; and it has been found at times also to fix thedye or color to perspiration, 'to wet and dry crocking, and t0 otherconditions involving resistance to the action of water, steam, andsaline solutions.

The present fixing composition enables the aftertreatment to becarriedout at relatively low temperatures, reducing the change of shade to aminimum, enabling economies in both time and steam to be secured and inaddition preventing .the deterioration of the materials and/or fabrics.

In practising the \invention, the dyed materials,

and especially the dyed union materials, after they have been washedclean of excess dye liquor are subjected to treatment with a preferredfixing composition.

The water soluble metallic salts, hitherto used in aftertreatment atelevated temperatures-as 7 'above set forth, when applied at relativelylow temperatures fix the dye of dyed materials to water and to wet hotpressing against white Thus bichrome fixes salts, as copper sulphate,bichromate of potash trated by the efiect of alum in aftertreatment.

The impregnation of the fiber with alum and the subsequent liberationand concentration of the sulphuric acid, or the acid constituents of thealum, during and after the drying of the goods makes tendering of thegoods inevitable: and as a result the use oi alum in the aftertreatmentof dyed union fabrics has geen generally abandoned.

The fixing composition which we prefer to employ comprises a mixture ofa water soluble salt, together with one or more reagents capable ofmodifying the action of the water soluble salt upon the fabric so thatthe resulting goods are free from the deleterious effects which thewater soluble salts by themselves may exert in tendering the fabric, incausing color changes, in finishing the fabric, etc.

We have discovered that the desirable efiects of water soluble salts infixing the color of the dye in dyed materials, and especially dyedunionmaterials, may be successfully utilized by m'odifying the watersoluble salt: firstly, with a reagent or reagents capable of suitablyaha-ting the acidity of the solution of the water soluble salt;secondly,

theoretically very great. However, practical and scientificconsiderations restrict the number that may be preferably employed. Thewater soluble salts of nearly all cations, especially the metalliccations,-fix colors more or less and in varying degrees. Acids, also,fix colors in varying degrees. The fixing action appears to be ametallic and/or acid effect.

The fixing power-of water soluble salts varies with the particularcation; and also in general increases with valence. monovalent cationshave a slight fixing power;

the salts of bivalent cations fix more readily;

and the more potentfixing salts are those of the trivalent and of thepolyvalent cations.

The fixing power of. acids varies with the dissociation, the morestrongly dissociated acids having the most eifect in fixing.

Anions influence the fixing variously, but their function appears to bemore an indirect one,

viz. to modify the action of the water soluble salts and chemicals. Ingeneral. the various anions influence the fixing in accordance with theprinciples of electrolytic dissociation and interaction. Thus saltsofstrong bases having acetic anions act as acid binders of ..salts ofstrong acids. The anion hydroxyl, the electrolytic opposite of thecation hydrogen, in excessive concentration is inimical to fixing.

Following is a list of salts, classified according to cations andanions,numerou's representatives of which we have investigated and foundto effect As a rule the salts of or influence variously the fixing ofthe dyes of dyed materials. 7

A. Cations.

1. Monovalent cations. Silver, sodium, and potassium salts, and hydrogensalts, or acids. Inasmuch as acids fix in varying degrees, the cationhydrogen is included in the list. Bivalent cations.

Copper, lead, cadmium, mercury, bismuth, tin, (stannous), iron(ferrous), zinc, nickel, cobalt, calcium, barium, and magnesium salts. v3. Trivalent cations.

Aluminum, chromium, iron (ferric) salts. 4. Polyvalent cations.

Tin (stannic), titanium (te'travalent), ce- ,rium salts.

B. Anions. I, Sulphates, basic sulphates, chlorides, nie

trates, fluorides, acetates, formates, tar-L trates, citrates,tungstates, chromates, di-

chromates, carbonates, borates, hydrox- W ater insoluble salts havelittle effectin fixing,

or at the most serve to modify the fixing. Thus, whereas the watersoluble chloride of barium readily fixes colors, the insoluble sulphateof barium has little if any effect. We prefer to utilize for the fixingcompositions the water soluble salts.

The effect other than fixing of the various salts as above classified ondyed materials varies with desirable efiects'varies greatly.

Practical and scientific considerations limit- 40 the number of watersoluble salts that may be tender fibers and to throw the shade, aswithdesirably employed as ingredients of the fixing composition: thus,high cost, as with silver, bis-' muth, cadmium, and cobalt salts; toxicconsiderations, as with lead salts; extreme tendency to stannicchloride; and tendency to reduce and destroy dyes, as with stannouschloride.

The most potent fixing agents are the salts of trivalent and ofpolyvalent. cations. After numerous experiments we have concluded thatthe The acid binding of the alum follows strictly the principles ofelectrolytic dissociation and interaction. Among acid binders may bementioned specifically alkalies and alkaline salts, as

soda ash, borax, and the like. In excess, however,

65 these alkaline reagents tend to destroy the fixing composition. Moresatisfactory as acid binders are the salts of strong bases and mildorganic acids, as sodium acetate, calcium acetate, sodium formate, andthe like. We have found the ace- 0 tates especially valuable as acidbinders, and in B are aifected variously by diflerent cations,

particular calcium acetate.

The principles of shade balancing as practised in making the preferredfixing compositions is of especial importance. The dyeings of certaindyes The principles of acid-binding and of shadebalancing are intimatelyintwined. The dyeings of many dyes :are sensitive to acids and theirshades are more or less changed or thrown by acid baths. Acid-bindingwill frequently coun teract most of the change of shade caused by fixingsalts that give in solution an acid bath.

In the listing above given most of the salts that fix can be utilized asshade balancers. However, in preparing the fixing compositions it ispreferable to select salts where the shade differences are not tooviolent and consequently diflicult to balance- Many of the salts in thelist above given combine all features: fixing, acid-binding, andshadebalancing. Such salts are .to be preferred as -modifiers of thealum. Among such salts, that we have found of especial value, arebasicsulphate of chromium and calcium acetate.

' Assistants that may be preferably included in the fixing compositionfacilitate additional desirable tendencies in. the process of fixing, as

evenness and penetration; and also Help in producing practicallyrequired properties in the fixed result, as freedom from crock, etc. Thesalts of tartaric, citric acid and the like, that might be expected fromgeneral experience to promote evenness, penetration, and freedom fromcrock, appear to be inimical to our main purpose of fixing'the colors,when used in relatively large proportions. Accordingly we have limitedsuch additions to relatively small proportions. We prefer to use forthis purpose bitartrateI of potash, and in particular a high grade ofargo Another assistant, the inclusion of which in the fixing compositionis more or less optional, is common salt. This assistant appears toprevent diffusion of the dye from the fiber back into the solution,assists perhaps somewhat in the levelling and penetration of the fixingand in imparting to finished goods a desirable feel. The pro portion ofcommon salt that we prefer to use is several times the amount of thefixing reagent,

and is best added in practising the process as will presently beexplained.

The ease of fixing colors varies greatly with the dyes. Thus, the,dyeings of the Direct Brown, Color Index No. 420, are quite readilyfixed, whereas the dyeings of the Direct Blue, Color Index No. 401,which is a favorite component of cheap navy. blue unionmixtures, arefixed with difliculty. Ease of fixing also varies with the character ofthe material: dyed materials ofall wool or practically all wool fix withless difficulty than dyed materials-containing cotton and/ or rayon, orcomposed entirely of cotton or rayon. The material appears to play apart, though an obscure one, in the fixing.-

While the preferring fixing compositions, containing as an essentialingredient the potent fixing salt alum, are required to fix the dyeingsthat are hard tdflx, dyeings that readily fix may be fixed by the use ofa less efiicient fixing composition than the preferred type by using asan essential ingredient a less potent fixing reagent than aluminumsulphate, and indeed various salts as above classified, and modifyingthem in accordance with the principles as above set forth. However, itis preferable to utilize in fixing dyeings easy to fix less of thepreferred fixing composition, which has specially been worked out forall-around use, for all dyes and materials.

Dyeings vary in their sensitiveness to acids and metals. Thus, thedyeings of the Direct Blue, Color Index No. 401, are extremely fasttoward strong acids, as sulphuric and hydrochloric, and even in stronglyacid baths their shades are little affected. On the other hand thedyeings of Direct Scarlet, Color Index No. 448, are sensitive toward andtheir shades are altered by acids, even mild organic acids.

In preparing the preferred fixing composition we have taken into accountthe various factors as above set forth. After numerous experiments wehave concluded that the best all-around fixing composition for generaluse comprises a water soluble sulphate of aluminum, modified withsuitable proportions of a basic sulphate of chromium, of calciumacetate, of argol, and of common salt.

The following formulas are illustrative examples of fixingcompositions'that may be utilized to practise the fixing of colors.

Formula 1 g Parts Aluminum sulphate 60 Calcium acetate 40 Formula 2Parts Aluminum sulphate 48 Calcium acetate 42 Common salt 10 Formula 3'Parts Aluminum sulphate 70 Basic chromium sulphate 10 Common salt 20Formula 4 Parts Aluminum sulphate; 48 Calcium acetate 12 Basic chromiumsulphate 12 Common salt 28 Formula 5 Parts Aluminum sulphate 48 Calciumacetate 12 Basic chromium sulphate- 12 Argols 4 Common salt 24 Formula 6Parts Aluminum sulphate 48 Calcium acetate 18 Basic chromium sulphate 12Argols 4 Common salt 18 Formula 7 Parts Aluminum sulphate 49 Calciumacetate 38 Basic chromium sulphate 9 Argols 4 while the foregoingrepresent typical compositions that may be employed in practise, it ispointed out that other proportions than those above given may be foundvadvantageous.

It is evident that in accordance with the principles above set forthfixing compositions can be utilized composed essentially of other watersoluble salts, as other aluminum salts and other salts as aboveclassified, to the extent that they are similar to and analogous inaction'in fixing to aluminum sulphate; that other acid binders analogousto and similar in action to calcium actate, as sodium acetate, can be beemployed;

that other salts than basic sulphate of chromium and calcium acetate, asferrous sulphate, similar in action and analogous in eifect as'shadebalancers can be utilized; that other tartrates or equivalents, asRochelle salt, similar to or analogous in action toargol can be used;and that other equivalents of common salt, as Glaubers salt, can beutilized.

It will also be understood that other water soluble salts of cations andanions not included in the above classification can be utilized ascomponents of a fixing composition to the extent that they are similarto and analogous in action to the-water soluble ,saltsas aboveclassified.

It will be readily understood that while-each of the ingredients of thefixing composition performs a specific function as above described,there I are probably actions and interactions-when all areblendedtogether and dissolved that produce practical resultsthat are superiorto those which might be ascribed separately to the individualconstituents of the fixing composition. For this reason the properproportions of the ingredients and their proper blending to produce afixing composition contribute to most eflicient use and to best results.

The preferred method of practising the use of the fixing compositionwill now be described, but it will be manifest to those skilled in theart that various practical variations of this method may be employed.

This process is simple to carry out and is especially distinguished bythe fact that it is practised at low and convenient temperatures.

Preferably the fixing composition should be dissolved in .a separatecontainer, and in practise the fixing composition selected may be dumpedinto a good sized barrel and coveredwith several pails of cold water;the whole is well stirred up and brought to a boil and boiled forfifteen minutes, stirring occasionally. This insures the solution of theingredients of the fixing compo- 1 sition and the completion ofessential chemical of the fixing compositions are included in this.

invention. We believe it to be preferable to blend the ingredientsbefore dissolving.

I 'As will be developed later, acetic or formic 15 acid can frequently"be used to advantage in conjunction with the fixing composition. In

such cases the acetic or formic acid, diluted in a pail of cold water,is added to the solution of the fixing composition, and the barrel isthen well 20 stirred and allowed to stand for a further five or tenminutes before using the fixing composition.

The dyed union goods having been thoroughly washed and'the fixingcomposition having been prepared as described, the preferred process of25 applicationcontinues as follows. The dyeing kettle with the wellwashed goods is filled witlf cold water; ten to fifteen percent ofcommon salt,

reckoned on the weight of the goods, is added to the bath; and the goodsrun in this solution for 30 five to ten minutes. This addition of salttends to prevent the thinning of the color on the cotton and to clear upthe excess dye liquor that may be leftin the kettle after the washing.It is also added for reasons previously explained.

Salt may be omitted if desired in the'fixing. However, we consider itsuse in conjoinhaction with the fixing composition preferable.

The fixing composition is then fed slowly to the dye-kettle in thecourse often minutes. This 40 is to ensure uniformity of fixation andpenetration of thefabric by the fixing chemicals as otherwise the actionof the fixing composition in concentrated solution would be too rapid.With the gradual addition of the fixing composition; the

45 liquor in the kettle begins to clear up from the final traces of dye,and the bath becomes virtually water white. I

After the fixing composition has been fed gradually tothe kettle, steamis turned on, and the bath is brought to 70 F.,about the temperature ofordinarysupply water in summer; and the fixing then continued forfifteen to twenty minutes. Running at a higher temperature, as l-l10 F.,may be advisable with certain fabrics difilcult to 55 penetrate. Theconditions of temperature best suited to any particular fabric can bedetermined by practical trials.

The quantity of fixing composition required to make dyed union fabricsfast to-water, wet hot 60 pressing against white fabrics, sometimes toperspiration, and to other conditions involving the action of water,steam, and saline conditions, depends on the depth of the'dyeing and thecharacter of the dyes. Light dyeings will require less 65 of the fixingcomposition than medium and heavy shade dyeings, and as has-already beenpointed out certain dyes fix relatively readily and others are hard tofix. Depending on the varying circumstances of the dyeing, the amountsof fixing 70 composition will vary from 1 /2 to 6 pounds per one hundredpounds, of dyed goods to be fixed.

In fixing it is advisable to use more fixing composition than willexactly fix the dye of the dyed goods. 75 scribed, there will be anexcess .of fixingcomposi- Accordingly, after fixing, as above detion inthe liquor of the kettle and also certain amounts of fixing compositionliquor loosely held in and on through the fibers of the fabric. It isessential to wash out of the bath and fabric the excess of fixingcomposition. There are several reasons forthis,-including a slightfurther elimi-- nation of acidity to fully insure safety in drying, andmore particularly for the reason to be presently explained. In thisregard we found in some,

examples, which appeared to be satisfactory, that the proper degree ofWashing was attained when the acidity of the materials and/or fabricshad been decreased to a point on the pH scale in the vicinity of 5 to 6.This frequently requires as thorough a washing as is commonly givenafter dyeing.

The reasons for these precautions become very manifest in. the fixing ofheavy weight fabrics and especially those that after drying and shearinghave to be heavily pressed. With such goods there is always a tendencyto stick to the presses, causing wrinkles, streaks or even eventuallytearing of the fabric. This tendency is accentuated if an excess offixing composition is left in the goods, as can occur if \they are notsufficiently washed afterfixing.

The principles enunciated for heavy weight fabrics apply. hough in a.lesser degree, to lighter weight goods. The amount and degree ofprecautions necessary for any fabric can be determined by practicaltrials. a

Acetic acid or, formic may be used in the fixin process for variousreasons. First, to neutralize any alkali that may be present in the dyedgoods. Alkali in the goods may come variously from insufficient washingafter fulling, or from the dye, or from alkaliused with the salt indyeing. The presence of alkali in the goods to be fixed tends to destroythe balances of thefixing composition.

reduce to a minimum the cost of fixing. It has been found that theaddition of acetic or formic acid to, the solution of the fixingcomposition makes it possible with some materials, as heavy meltons, toreduce the amount of fixing composition required to fasten the dyeing towater and to other conditions above indicated. Acetic or formic acid,furthermore, assists in reducing the ,sticking tendencies of goods inpressing.

In the above description of the practising of the use of the fixingcompositions, it was recoma fixing composition is illustrated by Formula#7 as above set forth. These special fixing compositions are preparedwith relatively larger proportions of acid binding ingredients, so thatthe acid of the alum, or other metallic salt, will be completelybufiered' even when not washed from the goods, the same principles beinginvolvedas in the preparation of all the fixing; compositions as I aboveset forth. I While a distinctive feature of the practising of the use oftheflxing compositions is their application, atilow temperatures, theymay .be also utilized at elevated temperatures, even at a boil, withcertain materials to advantage.

It will be understood that the words cotton and wool, as used throughoutthe specifications and claims are typical of and intended to definefibers that act in a general way similarly to cotton and wool; and thatthe words cotton and wool; cotton and mohair; cotton, wool, and silk;

' and various other blends may be fixed most effici'ently by the fixingcompositions above described. j

In this application the word materials is intended tomean ,in additionto union materials, single materials such as wool, cotton, rayon, silk,and leather, which may be dyed unfast to one or more of the aboverequirements, and which can be fixed advantageously by the use of ourfixing compositions.

The described use of the preferred types of fixing compositionspossesses a number of important commercial advantages as will beappre'ciated from the above description. These may be summed up asproducing dyed products, and

especially dyed union products, the 'dyeings of which are fast to water,to wet hot pressing against white, sometimes to perspiration, and toother similar agencies. In addition they prevent the tendering of thecotton and reduce change of shade to a minimum. A further practicaladvantageis that the specks of dyed union materials and/or fabrics arenot stripped in the use of our preferred types of fixing compositions,as in the 40 case of other fixing agents. The process can'be carried outin a comparatively short period of time, and at comparatively lowtemperatureathus effecting economies in time and steam as compared withprevious processes; and also saf guarding the texture of goods which aremore or less damaged by long treatments, particularly at'elevatedtemperatures, and therefore could not, prior to our invention, be safelyand satisfactorily fixed.

Another important practical advantage resulting from the use of thepreferred fixing compositions, as above set forth, is comparativeimmunity from undesirable accidental effects in the dyehouse. Thepreferred fixing compositions and especially those for leaving in thegoods, and the method of practising their use, as above set forth,appear to be virtually fool-proof. Thus, if in their practising thetemperature accidentally goes high, or if too much of the fixingcomposition is weighed out, or other and similar occasional errors orinfractions of the preferred method should occur, results inthe mainwill be satisfactory.

As used throughout the specifications and claims, the term "fix isintended to define the rendering of the dye in the dyed fibers permanentwith respect to its resistance to water, to wet hot pressing againstwhite, sometimes to perspiration, and to other similar agencies whichinvolve resistance to steam and saline solutions. 7 The term modifyingas used by us in the specifications and claims is intended to define andinclude acid-binding shade-balancing, abating,

modifying either in whole or in part, buffering,

and the other described effects upon the fixing agent and the goods.

treatment of dyedmaterials, including dyed union v materials, comprisingafixing reagent having as an essential component a water solublemetallic salt, which has a tendency to tender vegetable fiber and anacid binding agent.

2. A fixing composition for use in the aftertreatment of dyed materials,including dyed union materials, comprising a fixing reagent having as anessential component a water soluble sulphate of aluminum and an acidbinding agent.

3. A'fixing composition for use in the aftertreatment of dyed materials,including dyed union materials, comprising a fixing reagent having as anessential component a. water soluble sulphate of aluminum and an acidbinding agent including an acetate. 1

4. A fixing composition for use in the aftertreatment of dyed materials,including dyed union materials, comprising a fixing reagent having as anessential component a water soluble sulphate of aluminum and an acidbinding agent including calcium acetate.

5. A fixing composition for use in the after-" treatment of dyedmaterials, including dyed union materials, comprising a fixing reagenthaving as an essential component a water soluble metallic. salt, whichhas a tendency to throw the shade, and a shade balancing agentcomprising a water soluble metallic salt. v

6. A fixing composition for use in the after treatment of dyedmaterials, including dyed union materials, comprising a fixing reagenthaving as an essential component a water soluble metallic salt of atrivalent cation, which has a tendency to throw the shade, and a shadebalancing agent comprising a water soluble metallic salt.

7. A fixing composition for use in the aftertreatment of dyed materials,including dyed union materials, comprising a fixing reagent having as anessential component a water soluble sulphate of aluminum and a shadebalancing agent comprising a water soluble metallic salt.

8. A fixing composition for use in the aftertreatment of dyed materials,including dyed union treatment of dyed materials, including dyed unionmaterials, comprising-a fixing reagent having as an essential componenta water soluble metallic salt, which has a tendency to tender vegetablefiber and to throw the shade, and an acid bind- "ing agent, and a. shadebalancing agent comprising a water soluble metallic salt.

10. A fixing composition for usein the aftertreatment of dyed materials,including dyed union materials, comprising a fixing reagent having as anessential component a water soluble sulphate of aluminum and an acidbinding agent, and

the invention, what is a shade balancing agent comprising a watersoluble metallic salt.

11. A fixing composition for use in the aftertreatment of dyed material,including dyed union 10 materials, comprisinga fixing reagent having asan essential'co'mponent a water soluble sulphate of aluminum and acombined acid binding'and shade balancing agent comprising a watersoluble metallic salt. i

13. A fixing composition for use in the aftertreatment of dyedmaterials,including dyed union materials, comprising a major portion of "a watersoluble sulphate of aluminum and aminor portion of basic chromiumsulphate.

14. A fixing composition for use in the aftertreatment of dyed materialsincluding dyed union materials comprising a water soluble sulphate ofaluminum, calcium acetate and basic chromium sulphate.

15. Afixing .composition for use in the aftertreatment of dyed materialsincluding dyed union materials comprising a water soluble sulphate ofaluminum, calcium acetate, basic chromium sulphate, and an argol. j

1 6. In' the method of treating washed, dyed materials, the stepcomprising subjecting the dyed materials, including dyed unionmaterials, to treatment with a solution of a fixing reagent having as anessential component a water solu- 25 ble metallic salt, which has atendency to throw the shade, and a shade balancing agent compris-.

ing a water soluble metallic salt.

'17. In the method of treating washed dyed materials the step comprisingsubjecting the dyed materials, including dyed union materials, totreatment with a solution of a fixing reagent having as an essentialcomponent a water soluble m'etal-lic salt, which has a tendency totender vegetable fiber and to throw the shade,'and an acid bindingagent,and a shade balancing agent comprising a watersoluble metallic salt.

18. In the method of treating washed dyed materials, the step comprisingsubjecting the dyed materials, including dyed union materials,

5 to treatment at relatively low temperature with .a solution of afixing reagent having as an cs sential component a water solublemetallic'salt, which has a tendency to tender vegetable fiber and tothrow the shade, and an acid binding agent, and a shade balancing agentcomprising a water soluble metallic salt.

. 19. In the method of treating washed dyed materials, the stepcomprising subjecting the dyed materials, including dyed unionmaterials, to treatment at relatively low temperatures with a solutionof a fixing reagent having as an essential component a water solublesulphate of aluminum-and an acid binding agent, and a shade balancingagent comprising a water soluble metallic salt.

20. In the method of treating washed dyed materials, the step comprisingsubjecting the dyed materials, including dyed union materials,

'to treatment with a solution of a fixing reagent having asessential-components a water soluble sulphate of aluminum, an acidbinding agent comprising a water soluble metallic salt, a shadebalancing'agent, and a substantial proportion of Salt.

7 21. In the method of treatingwashed dyed materials, the stepcomprising subjecting the dyed materials to treatment with a solution ofa fixing reagent having as an essential component a water solublemetallic salt which has a tendency to tender vegetable fiber and tothrow the shade, an acid binding agent. a shade balancing agentcomprising a water soluble metallic salt and a substantial .proportionof common salt.

22.'In the method of treating washed dyed materials,. the stepcomprising subjecting the dyed materials to treatmentwith a solution ofa fixing reagent having as an essential component a Water solublemetallic salt which has a tendency to tender vegetable fiber and tothrow the shade, an acid binding agent, a shade balancing agentcomprising a water soluble metallic salt and a mild organic acid.

23. In the method of treating washed dyed

